Process of creaseproofing cellulosic fabrics with tetrakis (nu-methylolcarbamoylethyl) ethylenediamine



United States Patent m PRGCESE; 18h ENE (JELLULQSEQ FABRECS WETH TETP;AKlSN-WETHYLDLCAR- BAMGYLETHYLETHYLENEDlAMlNE Bethlehem K. Andrews, Metairie, and .lohn G. Erich, Jr., New @rlenns, La, assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed May 10, T1963, Ser. No. 284,768

ll Claim. (Cl. 8l16.3)

(Granted under Title 35', US. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United Stataes of America.

This patent application is a continuation in part of our co pending application Serial #115,269 (filed June 6, 1961), now US. Patent 3,167,384.

Cellulosic textiles are known to have an inherently poor ability to recover from undesirable wrinkling and creasing. There is a large demand for a treatment that will impart wrinkle resistance, and yet allow the textile to retain most of its original desirable characteristics.

Some of the existing treatments used are methylol derivatives of organic amides, formed from the reaction of formaldehyde with amides such as urea, melamine, and dicarboxylic acid diamides. After hypochlorite bleaching, however, textiles so treated often are susceptible to severe strength losses or suffer discoloration. To prevent this, treatments have been devised utilizing alkyl substituents on the amido nitrogen of the compound. These substituents replace any amido hydrogens remaining after the reaction with formaldehyde and thereby remove the groups that react with hypochlorites.

All of these sufier some disadvantages. For example, N,N-dimethyl diamido derivatives of dicarboxylic acids have been used to prepare the dimethylol compounds. These have reduced eliectiveness in producing desired wrinkle resistance.

Cyclic substituents such as in ethyleneurea have been used. The methylol derivative of this compound, dimethylol ethyleneurea, is highly effective in producing wrinkle resistance, and is initially resistant to damage from hypochlorite bleach. The finish, however, lacks durability to such acidic conditions as souring which is commonly encountered in many commercial iaundries. The immunity to hypochlorite bleaching is also lost on repeated laundering, with or without souring. The dimethylol triazones, another Widely known type of agent, contain a ter tiary amino group in the cyclic substituent. This tertiary amino group is believed to neutralize the eifects of hypochlorite bleaching. These compounds, however, produce a finish that is lacking in durability and is subject to discoloration on overheating, such as may occur on ironing.

It is the purpose of this invention to produce compounds of the organic amide class that can be used to impart durable wrinkle resistance finishes to celluosic textiles. The finish so produced will give a high degree of wrinkle resistance, withstand hypochlorite bleaching without damage to the treated textile, and be durable to laundering in which acidic or alkaline conditions are encountered.

The wrinkle resistance which is the subject of this invention is produced by the treatment of a cellulosic textile with the polymethylol derivative of a new class of polyamides of polycarboxylic acids which are unsubstituted on the amido nitrogen, and which contain a tertiary amino group in the carboxylic acid moiety. This tertiary amino group may be part of the alkyl chain joining the carboxyl groups or may be attached as a substituent 0n the chain. Even though these agents contain incompletely substituted amino groups, hypochlorite resistance is obtained in the fihzfilii Patented Aug. 24, 1%65 treated fabric, and the efiectiveness of the agent remains high.

Examples of the polyamides of this invention are: 1) Bis(carbamoylethyl)methylamine H NfiOH CH NCH -GH CNHi These compounds can be prepared by the reaction of the proper amine with the amide of a 1,2-unsaturated carboxylic acid. For example, the first of the above-mentioned compounds can be prepared by the reaction of methylamine with acrylamide:

These compounds can be converted to methylol derivatives by the reaction in aqueous solution of one or more moles of formaldehyde, or a substance that liberates formaldehyde, With one mole of the polyamide at pH 9-10. At least two moles formaldehyde are required to prepare the dimethylol compound, however, less can be used to prepare a partially methylolated compound. The lower methylol substitution causes reduced etfeotiveness, but may be desired in some instances where the highest wrinkle resistance is not required. The solution thus prepared is diluted to the padding concentration after standing at least four hours at the specified pH.

In accordance with the invention an aqueous solution is prepared as described above, containing from one to tweny percent of the reaction product containing two or more moles of formaldehyde in combination with one mole of the amide.

About 0.5 percent to 3 percent by weight of a catalyst, based on the total weight of the padding bath, is added to the padding bath to facilitate curing. Catalysts which can be used to promote curing include mineral acids; various salts of strong acids such as ammonium salts; alkanolamine salts; metallic salts of strong acids and weak bases, such as Zinc nitrate and magnesium chloride.

The treating solution of the methylol amide and catalyst, prepared as described above, is padded onto the cloth by passing through eiiicient squeeze rolls to give a wet pickup of sixty to one hundred percent. The curing step, the reaction of the methylol derivative of the polyamide with the textile, is carried out by the usual procedure. The padded textile is dried at an elevated temperature, for example 6070 C. for seven minutes, then further heated to effect the curing. Improved properties are obtained by curing at -160" C. from 0.5 to 10 minutes. The curing step is best followed by an afterwash with a detergent solution to remove any excess unreacted crease resistance agent, and to improve the hand of the textile.

The process and compounds to which this invention relates can be used to treat any hydrophilic fibrous cellulosic textile such as cotton, linen, ramie, jute, regenerated cellulose, and others.

Textiles treated according to the process of this inven tion are wrinkle resistant, andhave in additio-n washand-wear properties, that is, textiles so treated require no ironing after washing to maintain a'smooth appearance. They can be laundered and bleached in the manner used on untreated textiles without loss of properties or damageto the textile. e

The following examples are given as illustrations, and are not by any means intended to limit the scope of this invention. All percentages given in the examples are percentages by weight of the total solution. The fabrics were tested by the following methods: crease recovery angle, Monsanto method, American Society for Testing Materials (ASTM), Standards for Textile Materials D1295-53T; damage caused by retain-ed chlorine (scorch test), American Association of Textile Chemists and Colorists tentative test method 69-1952. The laundering procedure used to test the durability of the finish was the vigorous alkaline wash described in AATCC test method 14-53. V

EXAMPLE 1 Preparation of bis(carbamoylethyl)methylamine.

in methanol To 41 g. anhydrous methylamine dissolved in 160 g. methanol was added 199.6 g. acrylamide. The solution was allowed to stand at room temperature for seven days. The crude product, which separated from the solution melted at 113-120 C. Recrystallization from ethanol yielded 48 g. product melting at 114-116 C.

EXAMPLE 2 Preparation of bis(carbamylethyl)methylamine in water i To 38.7 g. 40% aqueous methylamine was added 71.2 g. acrylamide. The solution was stirred and kept below 10 C. throughout the addition. The solution was then allowed to come slowly to room temperature, and to stand stoppered at room temperature for two hours. The solution was evaporated to dryness under vacuum and the product recrystallized from a 3:1 acetone-alcohol mixture. Yield 70.0 g. M.P. 115-117 C. Percent yield 81%.

EXAMPLE 3 A 33 /3% solution of bis(N-methyloicarbamoylethyl) methylamine was prepared in the following manner: -bis(carbamoylethyl)methylamine was dissolved in 1.9 times its weight in water and suficient 36.3% formaldehyde solution added to afford a mole ratio of formaldehyde to bis(ca.rbamoylethyl)methylamine of 21' 1. This solution, pH 9.1, of 33 /3% solids concentration was allowed to stand overnight at room temperature. After this time the 33 /5 solution was diluted with suificient water to give a solids concentration, and 1.5% by weight of hydrated magnesium chloride (MgCl -6H' O) was added as catalyst, with sufficient 6 N HCl to make the solution to pH 4. The treating solution was padded onto a sample of 80 x 80 cotton print cloth to give a 70-80% wet pickup. The wet fabric was dried at original dimensions for seven minutes at 60 C.,,and then cured at original dimensions for three minutes at 160 C. The curing step was followed by an afterwash in warm water with a nonionic detergent added, and then tumble drying. The finished fabric possessed a crease recovery angle of 269 (warp-l-fill) while an untreated, afterwashed sample had a crease recovery angle of only 187 (warp-t-fill).

EXAMPLE 4 A sample of 80 x 80 cotton print cloth was treated with a 10% bis(N-rnethylol carbamoylethyl)methylamine w Z1 methylol dimethyl succinamide catalyzed by 0.5% zinc nitrate hexahydrate, were given 5 AATCC 14-53 washes. The effects of these Washes on the physical properties of the'finished fabrics are listed in Table I.

5 7 TABLE, 1

After 5 AATCC Original 14-53 washes Brk. str. ret. after AATCC 69-1952 scorch test, percent original 10 Brk. str.

Finishing agent used Crease ret. after 7 AATCC angle 69-1952 ((leg.) scorch test,

W+F percent original Crease rec. angle s) W +1? rec.

The finish produced by bis(N-methylol carbamoylethyl) methylamine is durable through the AATCC 14-53 washes. I

The finish is far superior in resistance to damage due to retained chlorine after 5 AATCC 14-53 alkaline washes than is thedimethylol ethyleneurea finish. The bis(N- methylol carbamoylethyl)methylamine finish is equal to or better than the triazone finish in durability, and does not discolor on heating as does the triazone finish. The dimethylol dimethyl succinamide finish shows no improvement in crease resistance over that of the untreated fabric. Table I shows that all the other attempts, mentioned earlier, to improve the-resistance to damage due to retained chloridean alkyl substituent on the amido nitrogen, a cyclicsubstituent on the amido nitrogens, and a cyclic substituent containing a tertiary amino grouphave either failed to produce a wrinkle resistance finish at all, produced a finishsusceptible to discoloration from heating, or produced a finish which, though initially accepta'ble,,will break down after launderings. Only the finish containing a tertiary amine in the carboxylic acid moiety, and no alkyl substituent on the amido groups is resistant to discoloration due to heat, and completely durable through the washes.

Example 5 The vigorous AATCC 14-53 washes are not the only conditions which may be encountered in the use of a textile. A wrinkle-resistance finish must also be durable through acidic conditions sometimes found in commercial laundries. Table II shows the wrinkle resistance of the bis(N-methylolcarbamoylethyl)rnethylamine finish, with that of two of the finishes listed in Table I, after exposure 7 to solutions of the indicated pHs at 40 C. for thirty minutes. The dimethylol ethyleneurea finish is removed at pH 3.0-3.5, and the triazone finish is removed at pH 2.5- 3.0. The fabric finished with bis(N-methylolcarbamoylethyl)methylamine shows no loss in wrinkle resistance or nitrogen content of the fabric (96% of the original nitrogen content retained) even at pH 1.

TABLE II Crease recovery angle (deg) W-l-F Finishing agent usedpH 1 pH 2.5 pH 3.5 pH 6 10% bis (N-methylol earbamoylethyl) methylamine 261 261 255 261 7}% dimethylol ethyleneurea 204 262 283 714% dimethylol ethyl triazone. 208 231 252 262 EXAMPLE 6 N,N,N,N tetralris(carbamoylethyl)ethylenediamine was prepared by the addition of 6 parts ethylenediamine in 6 parts Water to a solution of 28 parts acrylarnide in 14 parts Water. The mixture was cooled as the initial reaction proceeds and was allowed to stand overnight at room temperature. Filtering and drying the precipitated product yielded 23 parts of tetrakis (carbamoylethyl)ethylenediamine, melting range 167l7l C. Recrystallization of the product from ethanol gave a purer material, melting range 172-173 C., nitrogen content 24.20%.

A solution was prepared from 19.4 parts tetrakis(carbamoylethyl)ethylenediamine, 19.6 parts neutralized 36% formalin, and 40.4 parts Water. These quantities form a molar ratio of 4.2 formaldehyde to 1.0 tetrakis (carbarnoylethyl)ethylenediamine in a 33 /3 solution. The solution, of pH 8.7, was allowed to stand overnight to form tetrakis(N methylolcarbamoylethyl)ethylenediamine.

A treating solution containing approximately of the agent Was prepared by mixing parts of the 33% tetrakis(N methylolcarbamoylethyl)ethylenediarnine solution, 3 parts of a magnesium chloride hexahydrate solution, 67 parts Water, and suificient 6 N hydrochloric acid to make the solution pH 4.5. Cotton print cloth was padded with the treating solution to a 80% wet weight gain. The fabric was dried at 60 C. for 7 minutes, cured at C. for 3 minutes, washed in a Warm detergent solution, and dried. The untreated fabric had a crease recovery angle of 187, sum of wrap and filling values determined by the Monsanto tester. After treatment, the fabric had a crease recovery angle of 287 and retained 91% of its original strength in the AATCC test for resistance to retained chlorine.

To demonstrate the durability of the treatment the treated fabric was submitted to acidic and alkaline, hydrolytic conditions. The results, given in Table 111, show that the treatment has very high durability.

TABLE III After hydrolysis Hydrolysis for 30 minutes at 40 C. with pH- Chlorine r0sistance, percent strength retained Grease recovery angle, degrees We claim:

References Cited by the Examiner UNITED STATES PATENTS 2,203,493 6/40 Evans 81l6.3 2,294,43 5 9/ 42 Wolf 8116.3 2,856,427 10/58 Bruce et al 26056l 2,965,676 12/60 Fierce et a1. 260-561 3,048,620 8/ 62 Spivack.

3,167,384 1/65 Andrews et a1. 8-1163 FOREIGN PATENTS 1,072,982 12/59 Germany.

NORMAN G. TORCHIN, Primary Examiner. NICHQLAS S. RIZZO, Examiner. 

